CN111886131B - Barrier resin film, barrier laminate, and packaging material using the barrier laminate - Google Patents

Abstract

An object of the present invention is to provide a barrier resin film excellent in barrier properties without adopting a multilayer structure as in the prior art. A barrier resin film in which an aluminum oxide vapor-deposited film is formed on the surface of a resin base material, an element bonding structure represented by _Al3 is distributed in the above-mentioned aluminum oxide vapor-deposited film, and time-of-flight secondary ions The intensity ratio Al ₃ /Al ₂ O ₃ ×100 of the maximum Al ₃ concentration element bonding structure portion in mass spectrometry (TOF-SIMS) is 1 to 20.

Description

Barrier resin film, barrier laminate, and packaging material using the barrier laminate

technical field

The present invention relates to a barrier resin film and a barrier laminate excellent in oxygen and water vapor barrier properties that can be suitably used as packaging materials for electronic devices such as electronic paper, food, medicine, pet food, and the like, and a barrier laminate using the barrier laminate. Body packaging materials.

Background technique

In the fields of electronic devices such as electronic paper, food, and pharmaceuticals, in order to prevent the deterioration of the contents and maintain the functions and properties, it is necessary to stably exhibit higher barrier properties without being affected by temperature, humidity, etc. As for the laminated film, a barrier laminated film with a multilayer structure in which a barrier layer composed of a deposited film of silicon oxide, alumina, etc., and a barrier coating film layer is laminated on a resin substrate is also being developed.

For example, Patent Document 1 discloses a laminate comprising: a substrate made of a plastic material; a first vapor-deposited thin film layer disposed on the substrate; disposed on the first vapor-deposited thin film layer, A gas-barrier intermediate layer formed by coating a coating agent containing at least a water-soluble polymer; and a second vapor-deposited thin film layer provided on the intermediate layer; and further discloses a gas-barrier laminate, which An undercoat layer composed of a polyol, an isocyanate compound, and a silane coupling agent is provided between the substrate and the first vapor-deposited thin film layer.

Patent Document 2 discloses a high barrier sheet comprising: a base film made of synthetic resin; one planarization layer laminated on at least one surface of the base film; A gas barrier layer formed on the surface of an inorganic oxide or an inorganic nitride; and a sol/gel method laminated on the outer surface of the gas barrier layer by using a composition containing other metal alkoxides and/or hydrolyzates thereof formed planarization layer.

Patent Document 3 discloses a gas-barrier laminated film in which a metal oxide layer, a resin layer and a metal layer are laminated sequentially or in reverse order on the surface of a resin film, and the metal oxide layer is SiOx (1.0≤ Silicon oxide represented by x≤2.0).

However, the barrier laminated film of the above-mentioned multilayer structure not only increases costs such as raw material costs and equipment operation costs due to the increase in manufacturing steps, but also requires quality inspection of each layer. Complicated operations such as quality management revision and process management.

Therefore, a barrier film that can solve the above-mentioned problems in production without causing a decrease in productivity and has excellent barrier properties has been desired.

prior art literature

patent documents

Patent document 1: WO2002/083408 publication

Patent Document 2: Japanese Patent Laid-Open No. 2005-324469

Patent Document 3: Japanese Patent Laid-Open No. 2008-6762

Contents of the invention

The problem to be solved by the invention

The present invention was made to solve the above-mentioned problems, and provides a barrier resin film excellent in barrier properties without adopting a multilayer structure as in the prior art.

means to solve the problem

In order to achieve the above-mentioned problems, the barrier resin film of the present invention has a resin substrate and an aluminum oxide vapor-deposition film in which an element bonding structure represented by Al ₃ is locally distributed at a specific ratio on the resin substrate.

The ratio of the element-bonding structure represented by the above-mentioned Al ₃ is detected by etching the barrier resin film using time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the maximum intensity ratio Al ₃ /Al ₂ O ₃ ×100 is preferably More than 1 and less than 20.

That is, the present invention is characterized by the following aspects.

1. A barrier resin film comprising an alumina vapor-deposited film formed on a surface of a resin substrate, and further comprising a barrier coating layer adjacent to the surface of the alumina vapor-deposited film opposite to the resin substrate ,

In the above-mentioned aluminum oxide vapor _- deposited film, the element bonding structure represented by Al3 is distributed,

When the above-mentioned barrier resin film is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the intensity ratio Al ₃ /Al ₂ O ₃ ×100 of the maximum Al ₃ concentration element bonding structure in the aluminum oxide deposited film is 1 or more 20 or less.

2. The barrier resin film according to the above ₁ , wherein the maximum Al3 concentration element bonding structure part is present on the surface of the above-mentioned aluminum oxide vapor-deposited film opposite to the resin base material by a film thickness of the above-mentioned aluminum oxide vapor-deposited film 4% above 45% below the depth position.

3. The barrier resin film according to the above 1 or 2, wherein the surface of the resin substrate on which the aluminum oxide vapor-deposited film is formed is an oxygen plasma-treated surface.

4. The barrier resin film according to the above 3, wherein the aluminum oxide vapor-deposited film is formed in-line on the oxygen plasma-treated surface.

5. The barrier resin film according to any one of 1 to 4 above, wherein the resin base material contains a polyethylene terephthalate-based resin.

6. The barrier resin film according to any one of 1 to 5 above, wherein the resin base material contains a polybutylene terephthalate-based resin.

7. The barrier resin film according to any one of 1 to 6 above, wherein the resin base material contains a plant-derived polyester resin.

8. The barrier resin film according to any one of 1 to 7 above, wherein the resin base material contains a recycled polyester-based resin.

9. The barrier resin film according to any one of 1 to 8 above, wherein the barrier coating layer is made of a resin composition comprising a metal alkoxide and a hydroxyl-containing water-soluble resin having a degree of saponification of 90% to 100%. form.

10. The barrier resin film according to 9 above, wherein the mass ratio of the hydroxyl-containing water-soluble resin to the metal alkoxide, that is, hydroxyl-containing water-soluble resin/metal alkoxide, is 5/95 or more and 20/80 or less.

11. The barrier resin film according to 9 or 10 above, wherein the barrier coating layer has a thickness of not less than 150 nm and not more than 800 nm.

12. A barrier laminate comprising the barrier resin film and a sealant layer according to any one of 1 to 11 above.

13. A barrier packaging material produced from the barrier laminate described in 12 above.

14. A barrier packaging body made of the barrier packaging material described in 13 above.

The effect of the invention

According to the present invention, since a barrier resin film excellent in barrier properties is obtained without adopting a multilayer structure, a gas barrier film advantageous in terms of manufacture can be provided.

Description of drawings

FIG. 1 is a cross-sectional view showing an example of the barrier resin film of the present invention.

Fig. 2 is a cross-sectional view showing an example of another embodiment of the barrier resin film of the present invention.

Fig. 3 is a cross-sectional view showing an example of the barrier laminate of the present invention.

FIG. 4 is a plan view showing an example of an apparatus for forming an alumina vapor-deposited film in the present invention.

FIG. 5 is a graph analysis diagram showing an example of TOF-SIMS measurement results of the barrier resin film in the present invention.

detailed description

Hereinafter, the present invention will be described with reference to the drawings. However, the present invention is not limited to these specifically exemplified forms or various concretely described structures.

In addition, in each drawing, the size and ratio of a member may be changed or exaggerated for easy understanding. In addition, in order to make it easy to see, parts unnecessary for explanation and repeated symbols may be omitted.

<Barrier resin film>

As shown in FIG. 1 , the barrier resin film of the present invention includes: a layer composed of a resin substrate; an aluminum oxide vapor-deposited film formed on the layer composed of a resin substrate; Barrier coating.

In addition, although not shown, various functional layers may be laminated on the non-alumina vapor-deposited surface of the resin substrate and the non-alumina adhesive surface of the barrier coating layer as necessary.

The alumina vapor-deposited film in the present invention is not a simple alumina vapor-deposited film, but an element bonding structure represented by Al ₃ is distributed in the vapor-deposited film. Specifically, in the barrier resin film, an Al ₃ concentration element-bonding structure moiety indicating the presence of metallic aluminum was detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS), and its concentration was obtained as the detected intensity. The barrier resin film in the present invention is characterized in that the maximum strength ratio Al ₃ /Al ₂ O ₃ ×100 of the maximum Al ₃ concentration element bonding structure exhibiting the maximum strength is 1 to 20.

When the intensity ratio Al ₃ /Al ₂ O ₃ is less than the above-mentioned range, there are too few element bonding structures represented by Al ₃ in the vapor-deposited film, and the gas barrier property tends to decrease. When it exceeds the said range, the transparency of a vapor-deposition film will fall easily, the printability as a packaging material will be impaired, and the problem that the visibility of the content packaged as a packaging material will deteriorate easily will arise.

In addition, when the barrier resin film includes a barrier coating layer, it is possible to exhibit an oxygen transmission rate of 0.02 cc/m ² /day/atm or more and 0.2 cc/m ² /day/atm or less, a water vapor transmission rate of Barrier properties of 0.02 g/m ² /day or more and 0.2 g/m ² /day or less.

[Resin substrate]

The resin base material is not particularly limited, and known resin films or sheets can be used. For example, polyethylene terephthalate-based resins, polyesters derived from biomass, polybutylene terephthalate-based resins, polyethylene naphthalate-based resins, and the like can be used. Ester resins; polyamide resins including polyamide resin 6, polyamide resin 66, polyamide resin 610, polyamide resin 612, polyamide resin 11, polyamide resin 12, etc.; including polyethylene, polypropylene, etc. α- Polyolefin-based resins such as olefin polymers or copolymers; resin films.

Among these resins, polyester-based resins are preferably used, and among polyester-based resins, polyethylene terephthalate-based resins, polybutylene terephthalate-based resins, or plant-derived resins are more preferably used. polyester resins, and recycled resins of these resins can also be used. As the recycled resin, polyester-based resins, especially recycled resins of polyethylene terephthalate-based resins are preferable.

The resin base material may have a single layer or a multilayer structure of two or more layers, and in the case of a multilayer structure, layers of the same composition or layers of different compositions may be used.

In addition, in the case of a multilayer structure, an adhesive layer or the like may be interposed and bonded between the layers.

(polybutylene terephthalate (PBT) film)

Polybutylene terephthalate film has a high heat distortion temperature, excellent mechanical strength, excellent electrical properties, and good molding processability. When it is used for packaging bags containing food and other contents, it can suppress the heat loss caused by retort treatment. The packaging bag is deformed or its strength is reduced.

Polybutylene terephthalate film has high strength. Therefore, when the polybutylene terephthalate film is used, the packaging bag can be provided with puncture resistance similarly to the case where the packaging material constituting the packaging bag includes a nylon film.

In addition, since polybutylene terephthalate film is hydrolyzed in a high-temperature, high-humidity environment, a reduction in adhesion strength and barrier properties is observed after retort treatment, but it has a property of absorbing moisture less easily than nylon. Therefore, even when a polybutylene terephthalate film is arrange|positioned on the outer surface of a packaging material, it can suppress that the lamination strength between the packaging materials of a packaging bag falls. Due to this property, when polybutylene terephthalate film is used in retort packaging bags, it can replace the existing packaging materials of polyethylene terephthalate film and nylon film, so Can be used preferably.

The polybutylene terephthalate film is a film containing polybutylene terephthalate (hereinafter also referred to as PBT) as a main component, preferably 51% by mass or more, particularly preferably 60% by mass or more PBT resin film. In addition, the polybutylene terephthalate film is classified into two types by its structure.

The content of PBT in the polybutylene terephthalate film of the first aspect is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 75% by mass or more, most preferably 80% by mass or more.

In PBT used as a main constituent, terephthalic acid is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and most preferably 100 mol% as the dicarboxylic acid component. As a diol component, 1,4-butanediol is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more.

The polybutylene terephthalate film may contain polyester resins other than PBT. Polyester resins other than PBT include polyester resins such as PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polytrimethylene terephthalate (PPT). , can also include isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, cyclohexane dicarboxylic acid, adipic acid, azelaic acid, sebacic acid and other dicarboxylic acids copolymerized PBT Resin, or ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, poly PBT resin obtained by copolymerization of diol components such as ethylene glycol, polytetramethylene glycol, and polycarbonate diol.

It is preferable that the addition amount of these polyester resins other than PBT is 40 mass % or less. When the amount of the polyester resin other than PBT added exceeds 40% by mass, the mechanical properties as PBT are impaired, and impact strength, pinhole resistance, and deep-drawing formability are considered to be insufficient.

The layer structure of the polybutylene terephthalate film of the first aspect is produced by multilayering resins by a casting method and casting, and is composed of a multilayer structure part including a plurality of unit layers. Each of the plurality of unit layers contains PBT as a main component. For example, each of the plurality of unit layers contains 60% by mass or more of PBT. It should be noted that, among multiple unit layers, the n+1th unit layer is directly stacked on the nth unit layer. That is, no adhesive layer or bonding layer is interposed between the plurality of unit layers. Such a polybutylene terephthalate film is composed of a multilayer structure part including at least 10 or more unit layers, preferably 60 or more layers, more preferably 250 or more layers, and still more preferably 1000 or more unit layers.

The polybutylene terephthalate film of the second aspect is composed of a single layer including polyester having PBT as a main repeating unit. Polyesters with PBT as the main repeating unit include, for example, 1,4-butanediol or its ester-forming derivatives as a diol component, and terephthalic acid or its ester-forming derivatives as a dibasic acid component. Homopolymer or copolymer polyester obtained by condensing the main components. The content of PBT in the second constitutional form is preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or more.

The polybutylene terephthalate film of the second aspect may contain polyester resins other than PBT in a range of 30% by mass or less. By containing a polyester resin, crystallization of PBT can be suppressed, and the stretching processability of a polybutylene terephthalate film can be improved. As the polyester resin to be blended with PBT, polyester having ethylene terephthalate as a main repeating unit can be used. For example, a homopolymer type mainly composed of ethylene glycol as a diol component and terephthalic acid as a dibasic acid component can be preferably used.

The polybutylene terephthalate film of the second constitutional form can be produced by a tubular method or a tenter method. The unstretched base film may be stretched simultaneously in the longitudinal direction and the transverse direction by the tubular method or the tenter method, or may be sequentially stretched in the longitudinal direction and the transverse direction. Among them, the tubular method is particularly preferably employed because a stretched film having a good balance of physical properties in the circumferential direction can be obtained.

(polyester film from biomass)

The polyester film derived from biomass is composed of a resin composition comprising, as a main component, polyester composed of diol units and dicarboxylic acid units. The alcohol and dicarboxylic acid units are a resin composition of fossil fuel-derived dicarboxylic acid, more preferably a resin composition of biomass-derived ethylene glycol and fossil fuel-derived terephthalic acid.

Biomass-derived ethylene glycol has the same chemical structure as existing fossil-fuel-derived ethylene glycol, and therefore, membranes of polyester synthesized using biomass-derived ethylene glycol are comparable to existing fossil-fuel-derived polyester membranes. It is not inferior in terms of physical properties such as mechanical properties. Therefore, the barrier resin film of the present invention using a biomass-derived polyester film has a layer made of a carbon-neutral material, and therefore, compared with a conventional barrier resin film produced from a raw material obtained from fossil fuels, The consumption of fossil fuels can be reduced, and the environmental load can be reduced.

Biomass-derived ethylene glycol uses ethanol (biomass ethanol) produced from biomass such as sugar cane and corn as a raw material. For example, biomass-derived ethylene glycol can be obtained by producing ethylene glycol from biomass ethanol via ethylene oxide by a conventionally known method. In addition, commercially available biomass glycol can also be used, for example, biomass glycol commercially available from India Glycol can be used suitably.

Dicarboxylic acid derived from fossil fuels is used for the dicarboxylic acid component of polyester. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, Ethyl, Propyl and Butyl etc. Among these, terephthalic acid is preferable, and as a derivative of an aromatic dicarboxylic acid, dimethyl terephthalate is preferable.

As the resin substrate of the present invention, a single film made of biomass-derived polyester can be used. In addition, one of polyesters derived from biomass, and polyesters derived from fossil fuels, recycled polyesters derived from polyester products of fossil fuels, and recycled polyesters derived from polyester products derived from biomass can also be used. A film composed of one or more resins.

It is known that ¹⁴ C is contained in carbon dioxide in the atmosphere at a certain ratio (105.5 pMC). Therefore, the ¹⁴ C content in plants that absorb carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. In addition, it is also known that ¹⁴ C is hardly contained in fossil fuels. Therefore, by measuring the ratio of ¹⁴ C contained in all carbon atoms in polyester, the ratio of biomass-derived carbon can be calculated.

In the present invention, "biomass degree" means the weight ratio of biomass-derived components. Taking PET as an example, PET is a substance obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms at a molar ratio of 1:1, so only substances from biomass are used as ethylene glycol. In the case of alcohol, since the weight ratio of biomass-derived components in PET is 31.25%, the biomass is 31.25% (molecular weight of ethylene glycol derived from biomass/molecular weight of 1 polymerized unit of polyester=60÷ 192).

In addition, the weight ratio of the biomass-derived component of the polyester derived from fossil fuels was 0%, and the biomass degree of the polyester derived from fossil fuels was 0%. In the present invention, the biomass in the plastic substrate is preferably 5.0% or more, more preferably 10.0% or more, and preferably 30.0% or less.

(recycled PET)

As the resin base material of the present invention, one containing polyethylene terephthalate (hereinafter, polyethylene terephthalate is also referred to as PET) recycled by mechanical recovery can be used.

Specifically, the resin base material includes PET obtained by recycling PET bottles by mechanical recovery, in which the diol component is ethylene glycol, and the dicarboxylic acid component includes terephthalic acid and isophthalic acid.

Here, mechanical recycling generally refers to the method of pulverizing recycled PET bottles and other polyethylene terephthalate resin products, cleaning them with alkali, removing dirt and foreign matter on the surface of PET resin products, and then drying them under high temperature and reduced pressure. Press and dry for a certain period of time to diffuse and decontaminate the remaining pollutants inside the PET resin, remove the dirt from the resin product made of PET resin, and return to the PET resin again.

Hereinafter, in this specification, polyethylene terephthalate obtained by recycling PET bottles is referred to as "recycled polyethylene terephthalate (hereinafter also referred to as recycled PET)", Polyethylene terephthalate that is not recycled is called "virgin polyethylene terephthalate (hereinafter also referred to as virgin PET)".

In the PET contained in the resin base material, the content of the isophthalic acid component is preferably 0.5 mol% to 5 mol% and more preferably 1.0 mol% to 2.5 mol% of all dicarboxylic acid components constituting the PET.

When the content of the isophthalic acid component is less than 0.5 mol %, the flexibility may not be improved. On the other hand, if it exceeds 5 mol %, the melting point of PET may decrease and the heat resistance may be insufficient.

It should be noted that, in addition to PET derived from common fossil fuels, PET may also be biomass PET. "Biomass PET" contains ethylene glycol derived from biomass as a diol component and dicarboxylic acid derived from fossil fuels as a dicarboxylic acid component. The biomass PET may be formed only from PET containing ethylene glycol derived from biomass as a glycol component and dicarboxylic acid derived from fossil fuels as a dicarboxylic acid component, or may be composed of ethylene glycol derived from biomass and dicarboxylic acid derived from fossil fuels Diols are formed from PET having dicarboxylic acids derived from fossil fuels as dicarboxylic acid components as diol components.

PET used in PET bottles can be obtained by a conventionally known method of polycondensing the above-mentioned diol component and dicarboxylic acid component.

Specifically, after carrying out the esterification reaction and/or transesterification reaction of the diol component and the dicarboxylic acid component, it can be carried out by a general method of melt polymerization such as a polycondensation reaction under reduced pressure, or a method using an organic solvent. It can be produced by a known solution heating dehydration condensation method or the like.

With respect to 100 moles of dicarboxylic acid or its derivatives, the amount of the diol component used in the production of the above-mentioned PET is substantially equimolar. Usually, due to the presence of esterification and/or transesterification reaction and/or distillation in polycondensation reaction , so it is used in excess of 0.1 mol% or more and 20 mol% or less.

In addition, the polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and may be added in advance when the raw materials are charged, or may be added at the start of depressurization.

PET obtained by recycling PET bottles is polymerized and solidified as described above, and then, if necessary, solid-phase polymerization may be performed in order to further increase the degree of polymerization or to remove oligomers such as cyclic trimers.

Specifically, the solid-state polymerization is carried out in the following manner: After fragmenting PET and drying it, heating at a temperature of 100°C to 180°C for about 1 hour to 8 hours to pre-crystallize PET, and then, heating at 190°C The above-mentioned temperature of 230° C. or lower is carried out by heating under an inert gas atmosphere or under reduced pressure for 1 hour to several tens of hours.

The intrinsic viscosity of PET contained in the recycled PET is preferably not less than 0.58 dl/g and not more than 0.80 dl/g. When the intrinsic viscosity is less than 0.58 dl/g, the mechanical properties required for the PET film as a resin base material may be insufficient. On the other hand, when the intrinsic viscosity exceeds 0.80 dl/g, the productivity in the film forming process may be impaired. In addition, intrinsic viscosity was measured at 35 degreeC using the o-chlorophenol solution.

Recycled PET preferably contains recycled PET in a ratio of 50% by weight or more and 95% by weight or less, and virgin PET may be included in addition to recycled PET.

The virgin PET may be PET in which the above-mentioned diol component is ethylene glycol and the dicarboxylic acid component contains terephthalic acid and isophthalic acid, or PET in which the dicarboxylic acid component does not contain isophthalic acid. In addition, the resin base material layer may contain polyester other than PET. For example, as the dicarboxylic acid component, in addition to aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, aliphatic dicarboxylic acids and the like may be contained.

Specific examples of aliphatic dicarboxylic acids include common carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. A chain or alicyclic dicarboxylic acid whose number is 2 to 40. Examples of derivatives of aliphatic dicarboxylic acids include lower alkyl esters such as methyl, ethyl, propyl, and butyl esters of the above-mentioned aliphatic dicarboxylic acids, and cyclic anhydrides of the above-mentioned aliphatic dicarboxylic acids such as succinic anhydride. . Among these, adipic acid, succinic acid, dimer acid, or mixtures thereof are preferable as the aliphatic dicarboxylic acid, and those containing succinic acid as a main component are particularly preferable. As derivatives of aliphatic dicarboxylic acids, methyl esters of adipic acid and succinic acid, or mixtures thereof are more preferred.

The resin base material composed of such PET may be a single layer or a multilayer.

As shown in FIG. 2 , when the above-mentioned recycled PET is used as the resin base material, a three-layer resin base material including the first layer 2 a , the second layer 2 b , and the third layer 2 c can be produced.

In this case, it is preferable that the second layer 2b is a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 2a and the third layer 2c are layers composed of only virgin PET.

Thus, by using only virgin PET for the 1st layer 2a and the 3rd layer 2c, it can prevent that recycled PET protrudes from the surface or the back surface of a resin base material layer. Therefore, the sanitation of a laminated body can be ensured.

In addition, the resin base material layer may be a two-layer resin base material layer including the second layer 2b and the third layer 2c without providing the first layer 2a shown in FIG. 2 . Moreover, the resin base material layer may be a two-layer resin base material layer provided with the 1st layer 2a and the 2nd layer 2b, without providing the 3rd layer 2c shown in FIG. In these cases, it is also preferable that the second layer 2b is a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 2a and the third layer 2c are layers composed of only virgin PET.

In the case of mixing recycled PET and virgin PET to form a single layer, there are a method of separately supplying to a molding machine, a method of mixing and supplying by dry blending or the like, and the like. Among them, the method of mixing by dry mixing is preferable from the viewpoint of easy operation.

PET constituting the resin base material may contain various additives within the range not impairing its characteristics during the production process or after production. Examples of additives include plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weather-resistant agents, antistatic agents, linear friction reducers, mold release agents, antioxidants, ion Exchange agent, coloring pigment, etc. In the whole resin composition containing PET, it is preferable to contain an additive in the range of 5 mass % or more and 50 mass % or less, Preferably it is 5 mass % or more and 20 mass % or less.

The resin base material can be formed by forming a film using the above-mentioned PET, for example, by a T-die method. Specifically, after drying the above-mentioned PET, it is supplied to a melt extruder heated to a temperature (Tm) above the melting point of PET to a temperature of Tm+70° C., the resin composition is melted, and the resin composition is passed through a die such as a T die. It is extruded into a sheet, and the extruded sheet is quenched and solidified by a rotating cooling drum or the like to form a film. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder, etc. can be used according to the purpose.

The film obtained as described above is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded onto the cooling drum as described above is then heated by roller heating, infrared heating, etc., and stretched in the longitudinal direction to obtain a longitudinally stretched film. This stretching is preferably performed using a difference in peripheral speed between two or more rollers. The longitudinal stretching is usually carried out at a temperature range of 50°C to 100°C. In addition, the magnification of the longitudinal stretch depends on the required characteristics of the film application, and is preferably 2.5 times or more and 4.2 times or less. When the draw ratio is less than 2.5 times, the thickness unevenness of the PET film becomes large, making it difficult to obtain a favorable film.

The longitudinally stretched film is then sequentially subjected to the respective treatment steps of transverse stretching, heat setting, and thermal relaxation to become a biaxially stretched film. Transverse stretching is usually carried out at a temperature range of 50°C to 100°C. The transverse stretching ratio also depends on the required characteristics of the application, and is preferably 2.5 times or more and 5.0 times or less. When it is less than 2.5 times, the unevenness of the thickness of the film becomes large, making it difficult to obtain a good film; when it exceeds 5.0 times, breakage tends to occur during film formation.

After transverse stretching, heat setting treatment is carried out, and the temperature range of heat setting is preferably Tg+70～Tm-10°C of PET. In addition, the heat setting time is preferably not less than 1 second and not more than 60 seconds. Furthermore, for applications requiring a reduction in thermal contraction rate, thermal relaxation treatment may be performed as necessary.

The thickness of the PET film obtained as described above is optional depending on the application, but is usually about 5 μm to 100 μm, preferably 5 μm to 25 μm. In addition, the breaking strength of the PET film is 5 kg/mm ² to 40 kg/mm ^{2 in the MD direction, and 5 kg/mm 2 to} 35 kg/mm ² in the TD direction. In addition, the breaking elongation in the MD direction is Not less than 50% and not more than 350%, and not less than 50% and not more than 300% in the TD direction. In addition, the shrinkage rate when left to stand in a temperature environment of 150°C for 30 minutes is not less than 0.1% and not more than 5%.

It should be noted that the virgin PET may be fossil fuel polyethylene terephthalate (hereinafter also referred to as fossil fuel PET), or biomass PET. Here, "fossil fuel PET" means a diol derived from a fossil fuel as a diol component and a dicarboxylic acid derived from a fossil fuel as a dicarboxylic acid component. In addition, recycled PET may be obtained by recycling a PET resin product formed using fossil fuel PET, or may be obtained by recycling a PET resin product formed using biomass PET.

[Alumina vapor deposition film]

The aluminum oxide vapor-deposited film of the present invention is a thin film of an inorganic oxide containing aluminum oxide as a main component, and may contain a small amount of aluminum compounds such as aluminum nitrides, carbides, hydroxides, or mixtures thereof, silicon oxides, Metal oxides such as silicon nitride, silicon oxynitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, and zirconium oxide, or their metal nitrides, carbides, and mixtures thereof.

In the aluminum oxide vapor-deposited film of the present invention, the element bonding structure represented by Al ₃ is distributed, and the presence ratio of the element bonding structure represented by Al ₃ varies depending on the depth position of the aluminum oxide vapor-deposited film.

The presence ratio of the element bonding structure represented by Al ₃ can be expressed by the abundance ratio of Al ₂ O ₃ (alumina), and specifically, it can be detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) The ratio of the intensity of Al ₃ to the intensity of Al ₂ O ₃ is expressed by the intensity ratio Al ₃ /Al ₂ O ₃ .

The aluminum oxide vapor-deposited film of the present invention has a maximum Al ₃ concentration element bonding structure portion having an intensity ratio Al ₃ /Al ₂ O ₃ ×100 of 1 to 20. Therefore, the denseness of the deposited film is improved, and the gas barrier properties are improved.

In addition, the above-mentioned maximum Al concentration element _- bonding structure portion is preferably present at a depth of 4% to 45% of the film thickness of the above-mentioned alumina vapor-deposited film from the surface of the above-mentioned alumina vapor-deposited film on the opposite side to the resin substrate. .

With the above configuration, the outermost surface of the vapor-deposited alumina film becomes an alumina film having a degree of oxidation/hydroxide, adhesion to the barrier coating layer becomes favorable, and gas barrier properties are improved.

In addition, by providing the maximum Al3 concentration element bonding structure at a depth of ₄ % to 45% of the film thickness of the aluminum oxide vapor-deposition film, the density of the vapor-deposition film can be improved, and at the same time, it is possible to prevent penetration when the coating layer is laminated. The barrier coating material tends to react with aluminum, and the adhesion to the barrier coating layer becomes better.

The thickness of the aluminum oxide deposited film is preferably not less than 5 nm and not more than 100 nm. When it is less than the above range, the barrier properties are likely to be insufficient, and when it is more than the above range, the rigidity of the alumina vapor-deposited film is too strong, and peeling tends to easily occur.

[Method for forming aluminum oxide deposited film]

In the present invention, the aluminum oxide deposited film is preferably formed on the surface of the plasma-treated resin film, and the plasma treatment and the aluminum oxide deposited film forming process are performed using, for example, the deposition apparatus 10 shown in FIG. 4 .

In the vapor deposition apparatus 10 , partition walls 35 a to 35 c are formed in the decompression chamber 12 . The resin substrate transfer chamber 12A, the plasma pretreatment chamber 12B, and the film formation chamber 12C are formed by the partition walls 35a to 35c, and in particular, the plasma pretreatment chamber 12B and the film formation chamber 12B are formed as spaces surrounded by the partition walls 35a to 35c. The chamber 12C and each chamber further form an exhaust chamber inside as necessary.

(Oxygen plasma pretreatment)

In the present invention, by increasing the metal component in the alumina vapor-deposited film, the adhesion between the alumina vapor-deposited film and the substrate is likely to decrease, but the oxygen plasma pretreatment can improve the adhesion of the alumina vapor-deposited film on the interface side with the substrate. The degree of oxidation can improve the adhesion between the aluminum oxide deposited film and the substrate.

Therefore, in the oxygen plasma pretreatment, it is preferable to use simple oxygen or a mixed gas with an inert gas having a high partial pressure of oxygen as the supplied plasma source gas.

It is set so that the pretreated resin substrate S is conveyed into the plasma pretreatment chamber 12B, and a part of the plasma pretreatment roller 20 capable of plasma treatment is exposed to the resin substrate conveying chamber 12A, and the resin substrate S is on one side It moves toward the plasma preprocessing chamber 12B while being wound up.

The plasma pretreatment chamber 12B is configured to separate a space where plasma is generated from other areas, and the opposing space can be efficiently evacuated, thereby facilitating control of plasma gas concentration and improving productivity. The pretreatment pressure formed by decompression can be set and maintained at about 0.1 Pa to 100 Pa, particularly preferably 1 to 20 Pa.

The conveying speed of the resin substrate S is not particularly limited, but it can be at least 200 m/min to 1000 m/min, particularly preferably 300 to 800 m/min, from the viewpoint of production efficiency.

The plasma pretreatment unit includes a plasma supply unit and a magnetization unit. The plasma pretreatment unit cooperates with the plasma pretreatment roller 20 to seal the oxygen plasma P near the surface of the resin substrate S. Specifically, it is set up in the following manner: the plasma supply unit and the magnetic forming unit constituting the plasma pretreatment unit are arranged along the surface near the outer periphery of the pretreatment roll 20 to form the pretreated roll 20, the plasma supply The gaps sandwiched between the nozzles 22a-22c and the magnetization unit, the plasma supply nozzles 22a-22c also serve as electrodes for generating the plasma P while supplying the plasma source gas, and the magnetization unit has a function for promoting the plasma P. The resulting magnet 21 and so on.

The voltage between the pretreatment roller 20 and the plasma supply nozzles 22a to 22c is an AC voltage with a frequency of 10 Hz to 2.5 GHz and a voltage of 50 to 1000 volts, which is arbitrarily and stably applied by input power control or impedance control. state voltage.

The plasma supply unit of the plasma pretreatment unit includes: a raw material volatilization supply device 18 connected to a plasma supply nozzle provided outside the decompression chamber 12; and a raw material gas supply line from which raw material gas is supplied. The supplied plasma source gas is oxygen alone or a mixed gas of oxygen and an inert gas, and is supplied from a gas storage part by a flow controller while measuring the flow rate of the gas. Examples of the inert gas include one or a mixed gas of two or more selected from the group consisting of argon, helium, and nitrogen.

In order to form the aluminum oxide deposited film of the present invention, as oxygen plasma pretreatment, the mixing ratio of oxygen and the above-mentioned inert gas, oxygen/inert gas is preferably 6/1 to 1/1, more preferably 5/2 to 3 /2.

By making the mixing ratio 6/1 to 1/1, the film formation energy of vapor-deposited aluminum on the resin substrate increases, and by making it 5/2 to 3/2, the degree of oxidation of the aluminum oxide vapor-deposited film can be increased to ensure oxidation. Adhesion between aluminum vapor-deposited film and substrate.

As the plasma intensity per unit area used in the present invention, it is 50 to 8000W·sec/m ² , when it is 50W·sec/m ² or less, the effect of plasma pretreatment is not observed, and it is 8000W·sec/m 2 . When it is more than sec/m ² , there is a tendency for deterioration of the resin substrate due to plasma such as consumption of the resin substrate, damage and coloration, and firing. In particular, in order to form the aluminum oxide deposited film of the present invention, the plasma intensity of the plasma pretreatment is preferably 100 to 1000 W·sec/m ² .

(Formation of deposited film)

As a vapor deposition method for forming a vapor deposition film, various vapor deposition methods including physical vapor deposition methods and chemical vapor deposition methods can be applied. As the physical vapor deposition method, it can be selected from the group consisting of vapor deposition method, sputtering method, ion plating method, ion beam assisted method, and cluster ion beam method; as the chemical vapor deposition method, it can be selected from the group consisting of plasma CVD method, plasma In the group consisting of bulk polymerization method, thermal CVD method and catalytic reaction CVD method. In the present invention, a physical vapor deposition method is preferable.

The vapor deposition film forming device is arranged in the depressurized film forming chamber 12C, and evaporates the film forming roller 23 and the target material of the film forming source arranged opposite to the film forming roller to form a vapor deposition film on the surface of the resin substrate. The film roll 23 winds and conveys the resin base material S so that the treated surface of the resin base material S pretreated by the plasma pretreatment device is on the outside, and performs a film forming process.

The vapor deposition film forming unit 24 is a resistance heating method, uses aluminum as an evaporation source and uses an aluminum metal wire, supplies oxygen to oxidize the aluminum vapor, and forms an aluminum oxide vapor deposition film on the surface of the resin substrate S.

Oxygen can be supplied as a single substance of oxygen or as a mixed gas with an inert gas such as argon, and it is important to adjust the amount of oxygen that produces the maximum Al ₃ concentration element bonding structure.

Also, for example, in a boat-type (referred to as "boat-type") vapor deposition container, a plurality of aluminum metal wires are arranged in the axial direction of the roller 23 and heated by a resistance heating method, whereby aluminum can be evaporated.

In this way, the reaction between aluminum and oxygen can be controlled by evaporating the aluminum metal material while adjusting the supplied heat and heat, and adjusting the supplied oxygen amount, thereby forming the aluminum oxide vapor-deposited film of the present invention.

(Determination of the intensity ratio Al ₃ /Al ₂ O ₃ and the depth position of the element bonding structure at the maximum Al ₃ concentration)

In the present invention, the concentration of Al ₃ and the concentration of Al ₂ O ₃ in the aluminum oxide vapor-deposited film, and the depth position of the element-bonding structure at the maximum Al ₃ concentration are measured using TOF-SIMS, and the element-bonding structure at the maximum Al ₃ concentration is specified. The depth position, calculate the intensity ratio Al ₃ /Al ₂ O ₃ .

TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) is the following method: the primary ion beam is irradiated from the primary ion gun to the surface of the solid sample to be analyzed, and the time-of-flight difference (time-of-flight) is used proportional to the square root of the weight) mass-separate the secondary ions emitted from the surface of the sample by sputtering, and perform mass spectrometry analysis.

Here, by detecting the secondary ion intensity while performing sputtering, for the time-lapse data of the ion intensity of the secondary ion, that is, the ion of the element to be detected or the molecular ion bonded to the element to be detected, the elapsed time is converted into The concentration distribution of the detected element in the depth direction of the sample surface can be known.

In addition, the surface roughness meter is used to measure the depth of the depression formed on the surface of the sample by primary ion irradiation, and the average sputtering speed is calculated in advance from the depth of the depression and the elapsed time. Under the assumption that the sputtering speed is constant , the depth (sputtering amount) can be calculated from the irradiation time (that is, the elapsed time) or the number of irradiation cycles.

In the present invention, for the aluminum oxide vapor-deposited film of the laminated film, it is preferable to repeatedly perform soft etching at a constant rate using a Cs (cesium) ion gun as described above in order to measure the deepest region, and at the same time measure the Al ₃ , Al ₂ O ₃ ions in the layer and C ₆ ions from the resin substrate layer, so that the intensity ratio of each ion can be calculated.

In addition, by specifying the interface between the vapor-deposited aluminum oxide film layer and the resin base material layer, it can be known at what depth from the interface the maximum value of detected ions exists. That is, by defining the position at which the intensity of C ₆ ions reaches half of the maximum value as the interface between the resin substrate layer and the aluminum oxide layer, it can be known at what depth the detected ion intensity is located in the aluminum oxide layer .

The measurement results can be obtained, for example, as a graph shown in FIG. 5 . In the graph of FIG. 5 , the unit (intensity) of the vertical axis is the measured ion intensity, and the unit (cycle) of the horizontal axis is the number of times of etching.

Then, by obtaining the depth, Al ₃ intensity, and Al ₂ O ₃ intensity in the alumina vapor-deposited film in each cycle, the intensity ratio Al ₃ /Al ₂ O ₃ can be obtained, and the intensity ratio Al at which the maximum Al ₃ intensity can be calculated can be calculated. ₃ /Al ₂ O ₃ , and the ratio of the depth to the thickness of the aluminum oxide vapor-deposited film.

[Barrier coating layer]

The barrier coating layer protects the vapor-deposited alumina film mechanically/chemically and improves the barrier performance of the barrier resin film, and is formed adjacent to the vapor-deposited alumina film.

The barrier coating layer is formed from a coating agent for a barrier coating layer containing a metal alkoxide and a hydroxyl group-containing water-soluble resin. In the barrier coating layer, the metal alkoxide forms a condensation reaction product, but it may also form a co-condensation product with the hydroxyl-containing water-soluble resin.

The mass ratio of the hydroxyl group-containing water-soluble resin/metal alkoxide is preferably 5/95 or more and 20/80 or less, more preferably 8/92 or more and 15/85 or less. When it is less than the above range, the barrier effect of the barrier coating layer tends to be insufficient, and when it is greater than the above range, the rigidity and brittleness of the barrier coating layer tend to increase.

The thickness of the barrier coating layer is preferably not less than 150 nm and not more than 800 nm. When it is thinner than the above range, the barrier effect of the barrier coating layer tends to be insufficient, and when it is thicker than the above range, rigidity and brittleness tend to increase.

In the present invention, the barrier coating layer can be produced by the following method.

First, the above-mentioned metal alkoxide, hydroxyl-containing water-soluble resin, reaction accelerator (sol-gel method catalyst, acid, etc.) and organic solvents such as water, methanol, ethanol, isopropanol and other alcohols as solvents are mixed to prepare barrier properties. A coating agent composition for a coating layer.

Next, the aforementioned coating agent composition for a barrier coating layer is applied onto the alumina vapor-deposited film by a conventional method, followed by drying. Through this drying step, the above-mentioned condensation or cocondensation reaction further proceeds to form a coating film. The above coating operation may be further repeated on the first coating film to form a plurality of coating films consisting of two or more layers.

In addition, heat treatment is carried out at a temperature in the range of 20 to 200° C., preferably 50 to 180° C., and at a temperature not higher than the melting point of the resin base material for 3 seconds to 10 minutes. Thereby, a barrier coating layer can be formed on the alumina vapor-deposited film using the above-mentioned coating agent for a barrier coating layer.

It should be noted that the formation of the barrier coating layer is preferably performed in-line without contact with the outside air after the formation of the aluminum oxide vapor-deposited film.

(metal alkoxide)

The metal alkoxide has the general formula R ¹ nM(OR ² )m (wherein, R ¹ and R ² represent a hydrogen atom or an organic group with 1 to 8 carbon atoms, M represents a metal atom, and n represents 0 or more is an integer, m represents an integer of 1 or more, and n+m represents the atomic valence of M. Two or more R ¹ and R ² in one molecule may be the same or different).

Examples of specific metal atoms represented by M in the metal alkoxide include silicon, zirconium, titanium, aluminum, tin, lead, boron, and others. For example, an alkoxysilane in which M is Si (silicon) is preferably used.

Alkoxysilane is represented by the general formula R ¹ nSi(OR ² ) _m (where n+m=4).

In the above, specific examples of OR ² include hydroxyl, methoxy, ethoxy, n-propoxy, n-butoxy, isopropoxy, butoxy, and 3-methacryloyloxy. , 3-acryloyloxy and other alkoxy groups or phenoxy groups.

As mentioned above, specific examples of R include methyl, ethyl, ⁿ -propyl, isopropyl, phenyl, p-styryl, 3-chloropropyl, trifluoromethyl, vinyl, γ - Glycidoxypropyl, methacryloyl, γ-aminopropyl and the like.

Specific examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, Methyltrimethoxysilane, Methyltriethoxysilane, Methyltripropoxysilane, Methyltributoxysilane, Methyltriphenoxysilane, Phenylphenoxysilane, Ethyltrimethoxy Dimethylsilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethylsilane Oxysilane, Isopropyltriethoxysilane, Dimethyldiethoxysilane, Diphenyldimethoxysilane, Diphenyldiethoxysilane, Vinyltrimethoxysilane, Vinyltrimethoxysilane Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methyl Acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloyl Oxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, 1,6-bis(trimethoxysilane Various alkoxysilanes such as oxysilyl) hexane or phenoxysilane, etc.

In alkoxysilane, when R1 is ^an organic group with functional groups such as vinyl, epoxy, methacryloyl, amino, etc., it is usually called a silane coupling agent.

Specific examples of silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β-(3,4 - Epoxycyclohexyl)ethyltrimethoxysilane and the like, preferably γ-glycidoxypropyltrimethoxysilane.

The above-mentioned metal alkoxides may be used alone or in combination of two or more, and it is particularly preferable to use a silane coupling agent in combination. When using a silane coupling agent together, it is preferable to make 2 mass % or more and 15 mass % or less in all metal alkoxides to be a silane coupling agent.

(Hydroxy-containing water-soluble resin)

In the present invention, the hydroxyl-containing water-soluble resin is obtained by dehydration and co-condensation with metal alkoxide, and the degree of saponification is 90% to 100%, more preferably 95% to 100%, and even more preferably 99% to 100%. the following. When the degree of saponification is less than the above range, the hardness of the barrier coating layer tends to decrease.

Specific examples of hydroxyl-containing water-soluble resins include, for example, polyvinyl alcohol-based resins, ethylene/vinyl alcohol copolymers, polymers of bifunctional phenolic compounds and bifunctional epoxy compounds, and the like, which may be used alone or in Two or more types may be mixed and used, or may be used for copolymerization. Among these, polyvinyl alcohol is particularly preferable because of its excellent flexibility and affinity, and polyvinyl alcohol-based resins are suitable.

Specifically, for example, a polyvinyl alcohol-based resin obtained by saponifying polyvinyl acetate, and an ethylene/vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl acetate can be used.

Examples of such polyvinyl alcohol-based resins include RS resin "RS-110 (saponification degree = 99%, polymerization degree = 1,000)" manufactured by KURARAY Co., Ltd., "Gohsenol NM-14" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (saponification degree = 99%, polymerization degree = 1,400)" and the like.

<Barrier laminate>

As shown in FIG. 3 , the barrier laminate of the present invention is further laminated with at least a heat-sealable sealant layer on the barrier resin film of the present invention via an adhesive, or laminated without an adhesive. The outermost surface of the barrier laminate.

Furthermore, if necessary, a functional layer desired to be imparted when used as a packaging material, such as a light-shielding layer for imparting light-shielding properties, a printing layer for imparting decoration, printing, a pattern layer, a laser printing layer, an absorption or adsorption layer, may also be included. Various functional layers such as odor absorbing/absorptive layers are constituted as layers.

[Sealant layer]

The sealant layer may be a single layer, or may be composed of two or more layers. In the case of two or more layers, they may have the same composition or different compositions, and include only heat-sealable resins. A layer or a layer not containing a heat-sealable resin, and further includes a functional layer having various functions, and an adhesive layer, but the layer constituting the outermost layer on one side of the barrier packaging material preferably contains a resin with excellent heat-sealability.

In addition, the sealant layer may appropriately contain antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, antiblocking agents, flame retardants, crosslinking agents, colorants, pigments, lubricants, fillers, reinforcing agents, One or two or more of various inorganic or organic additives such as resins for modification. As its content, it can contain arbitrarily from a very small amount to several tens% according to the purpose.

For the sealant layer, a resin film using one or more heat-sealing resins, a resin coating film, or the like can be used.

<Barrier packaging material>

The barrier packaging material of the present invention is a packaging material made of a barrier laminate.

<Barrier package>

The barrier packaging body of the present invention is produced from the barrier packaging material of the present invention.

For example, barrier packages in the form of pillow bags, three-side seals, four-side seals, and gusset types can be produced by heat-sealing the sealant layer of the barrier packaging material.

Example

[Example 1]

<Formation of aluminum oxide deposited film>

First, a roll on which a polyester film (hereinafter referred to as PET film) having a thickness of 12 μm as a resin base material was wound was prepared.

Next, on the surface of the PET film on which the vapor-deposited film is provided, using a continuous vapor-deposited film-forming device that is equipped with a plasma pre-treatment device and separates the pre-treatment area and the film-forming area, the following plasma conditions are set in the pre-treatment area: The plasma is introduced from the plasma supply nozzle, and the plasma pretreatment is carried out at a conveying speed of 400m/min. In the continuous conveying film forming section, the plasma processing surface passes through the heating unit as a vacuum evaporation method under the following conditions A reactive resistance heating method was used to form a 12 nm-thick aluminum oxide vapor-deposited film on a PET film to obtain a roll of a barrier resin film, and various evaluations were performed.

(Plasma pretreatment conditions)

·Plasma intensity: 150W·sec/m ²

·Plasma forming gas ratio: oxygen/argon=2/1

・Applied voltage between pretreatment drum and plasma supply nozzle: 340V

· Vacuum degree of pretreatment area: 3.8Pa

(Alumina film formation conditions)

·Vacuum degree: 8.1×10 ^-2 Pa

·Conveying speed: 400m/min

・Oxygen gas supply: 8000 sccm

<Preparation of Barrier Coating Agent for Barrier Coating Layer>

In a solution adjusted to pH 2.2 by mixing 226 g of water, 39 g of isopropanol, and 5.3 g of 0.5N hydrochloric acid, 167 g of tetraethoxysilane was mixed while cooling to 10° C., to prepare a solution A.

Solution B was prepared by mixing 23.3 g of polyvinyl alcohol with a degree of polymerization of 2400 and a degree of saponification of 99% or more, 513 g of water, and 27 g of isopropanol.

Liquid A and liquid B were mixed at a weight ratio of 4.4:5.6, and the obtained solution was used as a barrier coating agent.

<Production of Barrier Resin Film with Barrier Coating>

The above-prepared barrier coating agent was coated on the aluminum oxide vapor-deposited film of the above-mentioned PET film by a spin coating method. Thereafter, heat treatment was performed in an oven at 180° C. for 60 seconds to form a barrier coating layer with a thickness of about 400 nm on the alumina vapor-deposited film to obtain a barrier resin film with a barrier coating layer.

[Example 2]

A barrier resin film and a barrier resin film with a barrier coating layer were obtained in the same manner as in Example 1 except that the supply amount of oxygen was 10000 sccm under the alumina film forming conditions.

[Example 3]

Except for the pretreatment in Example 1, a barrier resin film and a barrier resin film with a barrier coating layer were obtained in the same manner.

[Example 4]

A barrier resin film and a barrier resin with a barrier coating layer were obtained in the same manner as in Example 1, except that the base material was a plant-derived polyester resin, and the pretreatment plasma intensity was 250 W·sec/m ² . membrane.

[Comparative example 1]

A barrier resin film and a barrier resin film with a barrier coating layer were obtained in the same manner except that the amount of oxygen supplied under the alumina film formation conditions in Example 1 was 20000 sccm.

<Evaluation method>

[Intensity ratio Al ₃ /Al ₂ O ₃ in TOF-SIMS]

For the barrier resin film having a barrier coating layer, using a time-of-flight secondary ion mass spectrometer (manufactured by ION TOF, TOF. SIMS5), under the following measurement conditions, Cs (cesium ) ion gun repeated soft etching at a constant speed, and at the same time C ₆ (mass number 72.00) from the resin substrate, Al ₃ (mass number 80.94) and Al ₂ O ₃ (mass number 101.94) from the aluminum oxide vapor-deposited film, Mass spectrometric analysis of SiO ₂ (mass number 59.96) ions from the coating.

First, the position where the strength of the constituent element SiO ₂ of the barrier coating layer reaches half of the barrier coating layer is defined as the interface between the barrier coating layer and the aluminum oxide vapor-deposited film, and then the layer that reaches the constituent material C ₆ of the resin substrate Half of the position is used as the interface between the film base material and the aluminum oxide vapor-deposited film, and the first interface to the second interface are used as the alumina vapor-deposited film.

Then, the position where the intensity of Al ₃ is the highest in the alumina vapor-deposited film is obtained, and the intensity of Al ₃ at this position is calculated from the ratio Al ₃ /Al ₂ O _{3 of} the intensity of Al ₂ O ₃ to show the maximum The intensity ratio of Al ₃ /Al ₂ O ₃ , and the ratio of the depth to the thickness of the aluminum oxide vapor-deposited film.

TOF-SIMS measurement conditions

Primary ion species: Bi ₃ ⁺⁺ (0.2pA, 100μs)

·Measurement area: 150×150μm ²

Type of etching gun: Cs (1keV, 60nA)

·Etching area: 600×600μm ²

Etching rate: 10sec/Cycle

[Oxygen transmission rate]

Using an oxygen transmission rate measuring device (manufactured by MOCON Corporation, OX-TRAN2/21), the barrier resin film with a barrier coating layer is set so that the resin substrate side is the oxygen supply side, and measured according to JIS K 7126B method 23 Oxygen transmission rate in ℃, 100% RH atmosphere.

[Water Vapor Transmission Rate]

Using a water vapor transmission rate measuring device (manufactured by MOCON Corporation, PERMATRAN 3/33), set it so that the resin substrate layer side of the barrier resin film with a barrier coating layer is on the sensor side, and measure 37.8°C, Water vapor transmission rate under 100% RH atmosphere.

<Evaluation result>

In Examples 1 to 4, the intensity ratio Al ₃ /Al ₂ O ₃ ×100 in the maximum Al ₃ concentration element-bonding structure portion, which exists in the aluminum oxide evaporation, is ₁ to 20. At a depth of 4% to 45% of the film thickness of the plated film, the oxygen permeability and water vapor permeability are low, and good gas barrier properties are exhibited. In addition, compared to Example 3 with a plasma intensity of 0 (zero), Examples 1, 2, and 4 with a plasma intensity of 150 W·sec/m ² or more showed a stronger aluminum oxide vapor-deposited film/resin substrate tightness between.

On the other hand, in Comparative Example 1, the intensity ratio in the maximum Al concentration element _- bonded structure portion is less than 1, and there is no maximum Al concentration element _- bonded structure portion that satisfies the maximum intensity ratio of 1 to 20, and oxygen permeation High transmittance and water vapor transmission rate, showing poor gas barrier properties.

[Table 1]

Symbol Description

1 Barrier resin film

2 resin base layer

2a Resin substrate layer 1st layer

2b Resin substrate layer 2nd layer

2c Resin substrate layer 3rd layer

3 Aluminum Oxide Evaporated Film Layer

4 barrier coating

5 barrier laminate

6 layers of sealant

10-roller continuous vapor deposition film forming device

S resin substrate

P plasma

12 decompression chamber

12A Resin substrate transfer chamber

12B Plasma pretreatment chamber

12C film forming room

14a～d guide roller

18 Raw material gas volatilization supply device

20 pretreatment rolls

21 magnets

22 Plasma supply nozzle

23 film forming roller

24 Evaporation film forming unit

31 Power supply wiring

32 power supply

35a～35c next door

Claims (11)

1. A barrier resin film comprising a resin base material and, formed on the surface thereof, an aluminum oxide deposited film, and a barrier coating layer adjacent to the surface of the aluminum oxide deposited film on the opposite side of the resin base material,

the surface of the resin base material on which the aluminum oxide vapor-deposited film is formed is an oxygen plasma-treated surface,

the barrier coating layer is formed of a resin composition containing a metal alkoxide and a water-soluble hydroxyl group-containing resin having a saponification degree of 90% to 100%,

al is distributed in the aluminum oxide vapor deposition film ₃ The elemental bonding structures represented are shown as being,

when the barrier resin film is analyzed by using time-of-flight secondary ion mass spectrometry TOF-SIMS (time of flight-time ion mass spectrometry), the maximum Al in the aluminum oxide evaporation film ₃ Strength ratio Al of concentration element bonding structure portion ₃ /Al ₂ O ₃ X 100 is 1 to 20, and the maximum Al is ₃ The concentration element bonding structure portion is present at a depth position from the surface of the aluminum oxide deposited film on the opposite side to the resin base material, the depth position being 4% to 45% of the thickness of the aluminum oxide deposited film.

2. The barrier resin film according to claim 1, wherein the aluminum oxide deposited film is formed on the oxygen plasma-treated surface in an in-line manner.

3. The barrier resin film according to claim 1, wherein the resin base material comprises a polyethylene terephthalate-based resin.

4. The barrier resin film of claim 1, wherein the resin substrate comprises a polybutylene terephthalate-based resin.

5. The barrier resin film according to claim 1, wherein the resin base material comprises a plant-derived polyester-based resin.

6. The barrier resin film according to claim 1, wherein the resin base material comprises a recycled polyester-based resin.

7. The barrier resin film according to claim 1, wherein the mass ratio of the water-soluble hydroxyl group-containing resin to the metal alkoxide, that is, the water-soluble hydroxyl group-containing resin/metal alkoxide is 5/95 to 20/80.

8. The barrier resin film according to claim 1, wherein the thickness of the barrier coating layer is 150nm to 800 nm.

9. A barrier laminate comprising the barrier resin film of claim 1 and a sealant layer.

10. A barrier packaging material made from the barrier laminate of claim 9.

11. A barrier package made from the barrier packaging material of claim 10.

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